WO2008012275A1 - Nouveau procédé de production de biodiesel utilisant un catalyseur immobilisé - Google Patents

Nouveau procédé de production de biodiesel utilisant un catalyseur immobilisé Download PDF

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Publication number
WO2008012275A1
WO2008012275A1 PCT/EP2007/057528 EP2007057528W WO2008012275A1 WO 2008012275 A1 WO2008012275 A1 WO 2008012275A1 EP 2007057528 W EP2007057528 W EP 2007057528W WO 2008012275 A1 WO2008012275 A1 WO 2008012275A1
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WIPO (PCT)
Prior art keywords
oil
catalyst
minutes
methanol
tubular reactor
Prior art date
Application number
PCT/EP2007/057528
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English (en)
Inventor
Kathy Elst
Walter Adriansens
Louis Willems
Luc Van Ginneken
Original Assignee
Vlaamse Instelling Voor Technologisch Onderzoek (Vito)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Vlaamse Instelling Voor Technologisch Onderzoek (Vito) filed Critical Vlaamse Instelling Voor Technologisch Onderzoek (Vito)
Priority to PL07787777T priority Critical patent/PL2044183T3/pl
Priority to JP2009521239A priority patent/JP5484903B2/ja
Priority to BRPI0713194A priority patent/BRPI0713194B8/pt
Priority to EP07787777.7A priority patent/EP2044183B1/fr
Priority to CN2007800280284A priority patent/CN101495609B/zh
Priority to AP2009004736A priority patent/AP2963A/xx
Priority to AU2007278216A priority patent/AU2007278216B2/en
Priority to US12/374,644 priority patent/US8067624B2/en
Publication of WO2008012275A1 publication Critical patent/WO2008012275A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention is related to a process for producing fatty acid alkyl esters through a transesterification of triglyceride contained in a fat and oil by causing the fat and oil and an alcohol to react with each other.
  • the present invention discloses that the transesterification is performed in a tubular reactor containing an immobilized catalyst through which the raw materials are passed to react with each other.
  • European Patent EP 0985654B1 relates to a method for producing fatty acid esters from oil-and-fat and an alcohol by conducting a reaction under such conditions that at least one of the fats and oils and the alcohol is in a supercritical state in the absence of catalyst.
  • the prepared fatty acid esters are useful as fuels such as diesel fuels, lubrication base oils or fuel additives.
  • Saka and Kusdiana investigated transesterification of rapeseed oil in supercritical methanol in a one-step process without using any catalyst.
  • Experiments were carried out in a batch-type reaction vessel preheated at 350 and 400 0 C, at a pressure of 45-65 MPa, and with a molar ratio of methanol to rapeseed oil of 42:1.
  • the authors demonstrated that, in a preheating temperature of 350 0 C (at a pressure of 45 MPa) , 240 s of supercritical treatment of methanol was sufficient to convert the rapeseed oil to methyl esters (>95%) and that the prepared methyl esters were basically the same as those obtained by the conventional method with a basic catalyst.
  • reaction rate in methanol
  • the overall reaction was assumed to proceed as a first order reaction as a function of the concentration of triglycerides and reaction temperature.
  • T c 239.4°C
  • the reaction is limited by the low solubility of the alcohol in the triglycerides.
  • these mass transfer limitation are overcome because of the increased solubility and diffusivity of the supercritical fluid.
  • the reaction rate constant increases with about two orders of magnitude.
  • EP 1126011 describes a method in which a solid base catalyst is used in the production of fatty acid esters, at temperatures exceeding 260 0 C and in conditions wherein at least the oil or fat or the alcohol is in a supercritical state.
  • the alcohol used is methanol.
  • the critical temperature for methanol is about 240 0 C, while the critical pressure is about 80,9 bar. Oils or fats have higher critical points, and thus the minimum pressure disclosed in this application is 80, 9 bar.
  • US 5908946 discloses a method of production of acid esters from vegetable or animal oils and monoalcohols in the presence of a Zn-based catalyst. The reaction is carried out at a temperature between 170 0 C and 250 0 C and at a pressure of less than 100 bar.
  • the present invention relates to a method for the production of a fatty acid alkylester by transesterification of a fat or oil and an alcohol, wherein the reaction is catalysed by a (heterogeneous) catalyst immobilised in a tubular reactor, temperature is between 260 0 C and 420 0 C, pressure is higher than 5 bar, and a mixture of said fat or oil and said alcohol is led in a continuous flow through said tubular reactor.
  • the alcohol is methanol.
  • the catalyst preferably comprises (or consists of) a metal oxide. More preferably, the metal oxide comprises an alkaline earth metal. Be, Ca, Mg, Sr, Ba and Ra are alkaline earth metals. Even more preferably, the metal oxide comprises Mg. Alternatively, the metal oxide can comprise Ca. [0012] Preferably, in the method of the invention, the catalyst comprises (or consists of) MgO.
  • the catalyst comprises (or consists of) a metal carbonate. More preferably, the metal carbonate comprises an alkaline earth metal.
  • the alkaline earth metal is preferably Ca.
  • the catalyst preferably comprises (or consists of) CaC ⁇ 3.
  • the catalyst can also be a metal salt.
  • the catalyst can be a zeolite as well.
  • the catalyst is selected from the group consisting of CaCO3, MgO, ⁇ -A1203, Na2CO3, CaO and CaOH.
  • the catalyst is preferably immobilised in a fixed bed, as a powder, as pellets, as a coating or in a porous structure with a large specific surface.
  • the catalyst can be coated on a carrier.
  • the residence time of the mixture in the tubular reactor falls in the range between 1 minute and 100 minutes. More preferably, the residence time of the mixture in the tubular reactor falls in the range between 1 minute and 50 minutes.
  • the residence time of the mixture in the tubular reactor falls in the range between 1 minute and 45 minutes. More preferably, the residence time of the mixture in the tubular reactor falls in the range between 5 minutes and 25 minutes.
  • the residence time of the mixture in the tubular reactor falls in the range between 5 minutes and 15 minutes.
  • the contact time of said mixture with said catalyst is lower than 40 minutes and higher than or equal to 1 minute.
  • the contact time of said mixture with said catalyst is lower than 20 minutes and higher than or equal to 1 minute.
  • the contact time of said mixture with said catalyst falls in the range between 2 minutes and 8 minutes, more preferably in the range between 2 minutes and 6 minutes .
  • the pressure is lower than 80,9 bar, i.e. subcritical for methanol.
  • the pressure is between 5 and 400 bar, preferably between 5 and 150 bar, and more preferably between 40 and 80 bar.
  • the pressure falls in the range between 40 bar and 150 bar.
  • the ratio of alcohol versus fat or oil is preferably lower than 30 mole/mole.
  • this ratio can be lowered even more to less than 20, or less than 10 mole/mole.
  • the fat or oil can e.g. be selected from refined or unrefined fat or oil, and refined or unrefined waste fat or oil.
  • Fig. 1 represents the process according to the present invention.
  • the aim of the invention is met by processing the oil with MeOH in a continuous tubular reactor containing an immobilized catalyst.
  • the immobilized catalyst can be a metal-oxide but is not limited thereto.
  • methanol MeOH
  • other alcohols can be used as well in the method of the invention.
  • a heterogeneous catalyst refers to a catalyst that constitutes a separate phase (compared to the reactants) .
  • the catalyst materials of the invention can be mixed with each other and/or with other catalysts for use in the method of the invention.
  • the mixture of fat or oil and alcohol is applied to a reactor at a predetermined flow rate. Said mixture resides in the reactor for a period of time, referred to as the residence time.
  • the biodiesel was produced in a tubular reactor.
  • the reactor contained the immobilized heterogeneous catalyst.
  • One way of performing the immobilization is by physically enclosing the catalyst by filters. Of course, other immobilization techniques can be applied as well.
  • the set-up of the process is as follows: oil and alcohol are drawn from resp. reservoirs 3 and 1 using high pressure pumps 5 and brought to the desired pressure.
  • the alcohol is preheated in heater 7. Although not drawn, the oil can be preheated as well.
  • the mixed streams are passed through a tubular reactor 9 containing the immobilised catalyst.
  • the tubular reactor 9 is contained in a furnace or oil bath 11. After the reaction, the pressure is let off at pressure reduction valve 13, the product is cooled (15) and stored (17) .
  • Rapeseed oil and preheated methanol were compressed up to 150 bar and pumped in the tubular reactor. A correct mixing of both reactants was assured in the setup.
  • the mixed streams were heated up to 300 0 C in a furnace or oil bath and brought in contact with the immobilized heterogeneous catalyst. After contact, the resulting stream was cooled, depressurized and collected.
  • the tubular reactor used for the experiments comprises 3 sections: at the entrance a tubular part without catalyst, a fixed bed which can contain the immobilized (heterogeneous) catalyst and at the end again a tubular part without catalyst.
  • a first comparative example was made in a tubular reactor without fixed bed.
  • the total volume of the tubular reactor was 20 ml.
  • the methanol and oil were added at a rate ensuring a residence time of 10 minutes and a methanol-to-oil ratio of 0.46 g/g corresponding to a methanol excess of 13 mole/mole.
  • Comparative example 2. (C.2)
  • Comparative example 3 was made in the same reactor as comparative example 1 and 2. The flow rates of methanol and oil were adjusted to obtain a residence time of 20 minutes and a methanol-to-oil ratio of 0.7 corresponding to a methanol excess of 20. Comparative example 4. (C.4)
  • This comparative example was made in a tubular reactor containing the empty fixed bed.
  • the total empty volume of the reactor was 33 ml.
  • the methanol and oil were added at rates ensuring a residence time of 15 minutes and a methanol-to-oil ratio of 0.6 g/g corresponding to a methanol excess of 17 mole/mole.
  • the fixed bed was filled with CaCO3.
  • the empty volume of the reactor was 25 ml.
  • the flow rates were adjusted to achieve a residence time of 10 minutes and a methanol-to-oil ratio of 0.6 g/g
  • the fixed bed was filled with CaCO3.
  • the empty volume of the reactor was 25 ml.
  • the flow rates were adjusted to achieve a residence time of 5 minutes and a methanol-to-oil ratio of 0.6 g/g
  • the fixed bed was filled with MgO.
  • the total empty volume of the reactor was 25 ml.
  • the flow rates were adjusted to achieve a residence time of 10 minutes and a methanol-to-oil ratio of 0.6 g/g Invention example 4 (1.4)
  • the fixed bed was filled with MgO.
  • the total volume of the reactor was 25 ml.
  • the flow rates were adjusted to achieve a residence time of 5 minutes and a methanol-to-oil ratio of 0.6 g/g
  • the fixed bed was filled with ⁇ -A1203.
  • the total volume of the reactor was 25 ml.
  • the flow rates were adjusted to achieve a residence time of 15 minutes and a methanol-to-oil ratio of 0.6 g/g
  • the biodiesel content was measured through GC-analysis .
  • the table lists the conversion rate, which corresponds to the amount of biodiesel in the distilled reaction product after separation of the glycerol fraction. [0050] The table clearly shows higher conversion rates for the invention, although lower reaction times (residence times) were applied.
  • the biodiesel was produced in a tubular reactor.
  • the reactor contained the immobilized heterogeneous catalyst and had an empty value of 15 ml.
  • the immobilization was performed using pressed MgO pellets with a diameter of 2 cm and a thickness of 1 cm. Rapeseed oil and preheated methanol were compressed up to the required pressure and pumped in the tubular reactor. A correct mixing of both reactants was assured in the set-up.
  • the mixed streams were heated up to the required temperature in a furnace or oil bath and brought in contact with the immobilized heterogeneous catalyst. After contact, the resulting stream was cooled, depressurized and collected.
  • Invention example 11 (1.11) [0057] The methanol and oil were added to the tubular reactor and the flow rates were adjusted to achieve a residence time of 10 minutes and a methanol-to-oil ratio of 0.6 g/g. The process temperature was 240 0 C and pressure was 150 bar. Invention example 12 (1.12)
  • the biodiesel was produced in a tubular reactor.
  • the reactor contained the immobilized heterogeneous catalyst and had an empty value of 15 ml.
  • the immobilization was performed using pressed MgO pellets of a size of 2 cm diameter and 1 cm thickness.
  • the oil and preheated methanol were compressed up to 150 bar and pumped in the tubular reactor. A correct mixing of both reactants was assured in the set-up.
  • the mixed streams were heated up to 300 0 C in a furnace or oil bath and brought in contact with the immobilized heterogeneous catalyst. After contact, the resulting stream was cooled, depressurized and collected.
  • the biodiesel was produced in a tubular reactor.
  • the reactor contained the immobilized heterogeneous catalyst and had a total empty value of 15 ml.
  • the immobilization was performed using pressed MgO pellets of a size of 2 cm diameter and 1 cm thickness.
  • the oil and preheated methanol were compressed up to 150 bar and pumped in the tubular reactor. A correct mixing of both reactants was assured in the set-up.
  • the mixed streams were heated up to 300 0 C in a furnace or oil bath and brought in contact with the immobilized heterogeneous catalyst. After contact, the resulting stream was cooled, depressurized and collected.
  • Ratio fixed bed / empty reactorvolume [0067] The biodiesel was produced in a tubular reactor.
  • the reactor comprises 3 sections: at the entrance a tubular part without catalyst, a fixed bed containing the immobilized heterogeneous catalyst and at the end again a tubular part without catalyst.
  • the immobilization was performed using pressed MgO pellets of a size of 2 cm diameter and 1 cm thickness.
  • the oil and preheated methanol were compressed up to 150 bar and pumped in the tubular reactor. A correct mixing of both reactants was assured in the set-up.
  • the mixed streams were heated up to 300 0 C in a furnace or oil bath and brought in contact with the immobilized heterogeneous catalyst. After contact, the resulting stream was cooled, depressurized and collected.
  • the biodiesel was produced in a tubular reactor.
  • the reactor contained the immobilized heterogeneous catalyst and had an empty value of 15 ml.
  • the immobilization was performed using pressed MgO pellets with a diameter of 2 cm and a thickness of 1 cm. Rapeseed oil and preheated methanol were compressed up to the required pressure and pumped in the tubular reactor. A correct mixing of both reactants was assured in the set-up.
  • the mixed streams were heated up to the required temperature in a furnace or oil bath and brought in contact with the immobilized heterogeneous catalyst. After contact, the resulting stream was cooled, depressurized and collected. [0070] To show that the process also works with a small excess of methanol, several examples are shown:
  • the contact time is defined as (see US 5908946) the ratio of the volume of catalyst in the reactor to the volumetric flow rate of the alcohol and the oil or fat (the reactants) applied to the reactor.
  • the ratio has the unit of time and can be regarded as an indication of the time the reactants are in contact with the catalyst.
  • the relation between residence time and contact time can be derived when one considers that the residence time refers to the ratio of the empty (free) volume of the reactor to the volumetric flow rate of the alcohol and the oil or fat to the reactor.
  • the empty volume of the reactor refers to the volume of the reactor without the catalyst being loaded minus the volume taken by the catalyst .
  • the ratio of contact time to residence time equals the ratio of volume of catalyst to empty volume of the reactor.
  • the contact time is typically smaller than the residence time, as the empty volume of the reactor is typically larger than the volume of catalyst.
  • the volumetric flow rate of the reactants can be calculated from a mass flow rate based on atmospheric conditions .
  • the contact times in examples 1.6 to 1.15 equal the residence time multiplied by 0.4.
  • the contact time is 6 minutes.
  • the contact time is 4 minutes.
  • the process of the invention works at short contact times. This is a significant economical advantage for the process, because it allows higher production rates and uses less catalyst with a fixed installation.
  • the flow rates were adjusted to have a residence time of 68 minutes, corresponding to a contact time of 17 min.
  • the process conditions such as temperature, pressure and oil/methanol ratio were taken very similarly to the conditions described in the above patent (see table 4 of US 5908946) .
  • the process conditions of the present example were as follows: pressure of 50 bar, a temperature of 240 0 C, and a MeOH-excess of 0.6 g/g, which corresponds to a volumetric oil/alcohol-ratio of 1.4. A conversion efficiency of 98% was achieved.
  • Invention example 22 (1.22)
  • the present example is to prove that the process of the invention works at small contact times, without significant magnesium in the product stream.
  • the biodiesel was produced in a tubular reactor. Oil and methanol were fed to the tubular reactor. The reactor contained 15 g of fused MgO - mesh 4. The catalyst volume was 4.2 ml. The empty volume of the reactor was 16.9 ml. The flow rates were adjusted to have a residence time of 16 minutes, corresponding to a contact time of 4 minutes. The reaction was performed at 32O 0 C and 150 bar and a MeOH-excess of 0.6 g/g. The conversion efficiency was 99%+/- 3%. In the undestilled product stream, Mg could not be detected, which refers to less than 5 ppm Mg .
  • Biodiesel was produced in a tubular reactor.
  • the reactor contained 81.4 g of dead-burned MgO of mesh 30.
  • the catalyst volume was 23 ml.
  • the empty volume of the reactor was 210 ml.
  • the flow rates of the oil and methanol were adjusted to have a residence time of 20 minutes, corresponding to a contact time of 2 minute.
  • the reaction was performed at 33O 0 C and 150 bar and a MeOH-excess of 0.61 g/g.
  • the conversion efficiency was 98% +/- 4 %.
  • Biodiesel was produced in a tubular reactor containing 58.6 g of dead burned MgO of 3-5 mm.
  • the catalyst volume was 16.5 ml.
  • the empty volume of the reactor was 216 ml.
  • the flow rates of the oil and methanol were adjusted to have a residence time of 28 minutes, corresponding to a contact time of 2 minutes.
  • the reaction was performed at 340 0 C and 150 bar.
  • the MeOH-excess was 0.6 g/g.
  • the conversion efficiency was 95% +/-4%.
  • the biodiesel was produced by feeding oil and methanol to a tubular reactor containing 58.9 g of dead burned MgO of 0.5-1 mm.
  • the catalyst volume was 16.5 ml.
  • the empty volume of the reactor was 18.2 ml.
  • the flow rates were adjusted to have a residence time of 18 minutes, corresponding to a contact time of 16 minutes.
  • the reaction was performed at 310 0 C and 150 bar.
  • the MeOH-excess was 0.6 g/g.
  • the conversion efficiency was 100% +/-3%.
  • the biodiesel was produced in a tubular reactor.
  • the reactor contained immobilized MgO-Al2 ⁇ 3 ⁇ Zr ⁇ 2 catalyst (99% purity) and had an empty volume of 15 ml.
  • the reactor was loaded with 10 g of sintered lumps of 1-3 mm.
  • the catalyst had a volume of 2.8 ml.
  • the empty volume of the reactor was 18.3 ml.
  • the oil and preheated methanol were compressed up to 150 bar and pumped in the tubular reactor.
  • the flow rates were adjusted to achieve a residence time of 18 minutes and a MeOH-excess of 0.6 g/g. A correct mixing of both reactants was assured in the setup.
  • the mixed streams were heated up to 340 0 C in a furnace or oil bath and brought in contact with the immobilized heterogeneous catalyst. After contact, the resulting stream was cooled, depressurized and collected.
  • the fixed bed was filled with immobilized fused Al 2 MgO 4 with a particle size of 1-3 mm.
  • the catalyst weighed 9.3 g and had a volume of 2.6 ml.
  • the empty volume of the reactor was 18.5 ml.
  • the flow rates were adjusted to achieve a residence time of 19 minutes and a MeOH-excess of 0.6 g/g.
  • the contact time amounted 2.6 min.
  • the reaction was performed at 150 bar and 32O 0 C.
  • the conversion efficiency amounted 97% +/- 3%.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production d'un alkylester d'acide gras par transestérification d'une matière grasse ou d'une huile et d'un alcool, selon lequel la réaction est catalysée par un catalyseur hétérogène immobilisé dans un réacteur tubulaire, la température étant comprise entre 260 et 420 °C, la pression étant supérieure à 5 bars, et un mélange de ladite matière grasse ou huile et dudit alcool est introduit en un flux continu dans ledit réacteur tubulaire. Le catalyseur est de préférence un oxyde métallique ou un carbonate métallique comprenant un métal alcalino-terreux. La réaction a lieu avec des temps de séjour et des temps de contact réduits en comparaison de l'art antérieur.
PCT/EP2007/057528 2006-07-26 2007-07-20 Nouveau procédé de production de biodiesel utilisant un catalyseur immobilisé WO2008012275A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
PL07787777T PL2044183T3 (pl) 2006-07-26 2007-07-20 Nowy sposób wytwarzania biodiesla z użyciem unieruchomionego katalizatora
JP2009521239A JP5484903B2 (ja) 2006-07-26 2007-07-20 固定化触媒を使用してバイオディーゼルを製造するための新規な方法
BRPI0713194A BRPI0713194B8 (pt) 2006-07-26 2007-07-20 método para a produção de um éster alquílico de ácido gorduroso por transesterificação de um óleo ou gordura e um álcool
EP07787777.7A EP2044183B1 (fr) 2006-07-26 2007-07-20 Méthode de production de biodiesel utilisant un catalyseur immobilisé
CN2007800280284A CN101495609B (zh) 2006-07-26 2007-07-20 使用固定的催化剂生产生物柴油的新方法
AP2009004736A AP2963A (en) 2006-07-26 2007-07-20 Novel method for producing biodiesel using an immobilised catalyst
AU2007278216A AU2007278216B2 (en) 2006-07-26 2007-07-20 Novel method for producing biodiesel using an immobilised catalyst
US12/374,644 US8067624B2 (en) 2006-07-26 2007-07-20 Method for producing biodiesel using an immobilised catalyst

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06117908.1 2006-07-26
EP06117908A EP1884559A1 (fr) 2006-07-26 2006-07-26 Méthode de production de biodiesel utilisant un catalyseur immobilisé

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WO2008012275A1 true WO2008012275A1 (fr) 2008-01-31

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PCT/EP2007/057528 WO2008012275A1 (fr) 2006-07-26 2007-07-20 Nouveau procédé de production de biodiesel utilisant un catalyseur immobilisé

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US (1) US8067624B2 (fr)
EP (2) EP1884559A1 (fr)
JP (2) JP5484903B2 (fr)
CN (1) CN101495609B (fr)
AP (1) AP2963A (fr)
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101624533A (zh) * 2008-07-12 2010-01-13 程文波 一种生物柴油生产中酯交换反应方法及其装置
WO2010085947A1 (fr) 2009-01-30 2010-08-05 Hoelderich Wolfgang Friedrich Procédé de production d'esters d'acides gras et de glycérol par transestérification de graisses et d'huiles végétales et animales
US7897798B2 (en) 2006-08-04 2011-03-01 Mcneff Research Consultants, Inc. Methods and apparatus for producing alkyl esters from lipid feed stocks and systems including same
US7943791B2 (en) 2007-09-28 2011-05-17 Mcneff Research Consultants, Inc. Methods and compositions for refining lipid feed stocks
US8017796B2 (en) 2007-02-13 2011-09-13 Mcneff Research Consultants, Inc. Systems for selective removal of contaminants from a composition and methods of regenerating the same
US8070836B2 (en) 2007-10-16 2011-12-06 Wayne State University Combined homogeneous and heterogeneous catalytic transesterification process for biodiesel production
US8163946B2 (en) 2008-05-19 2012-04-24 Wayne State University Methods and catalysts for making biodiesel from the transesterification and esterification of unrefined oils
US8361174B2 (en) 2008-10-07 2013-01-29 Sartec Corporation Catalysts, systems, and methods for producing fuels and fuel additives from polyols
US8445709B2 (en) 2006-08-04 2013-05-21 Mcneff Research Consultants, Inc. Systems and methods for refining alkyl ester compositions
US8585976B2 (en) 2007-02-13 2013-11-19 Mcneff Research Consultants, Inc. Devices for selective removal of contaminants from a composition
WO2014094007A2 (fr) 2012-12-18 2014-06-26 Gerhard Nauer Procédé de production d'un carburant biodiesel à l'aide d'un réacteur de conception spéciale, dont le matériau présente une surface à structuration nanométrique ayant un effet „(auto)catalytique"
US8895764B2 (en) 2008-05-19 2014-11-25 Wayne State University ZnO nanoparticle catalysts for use in biodiesel production and method of making
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DE102006047617B4 (de) 2006-10-09 2008-11-27 Clariant International Limited Verfahren zur Herstellung basischer (Meth)acrylamide
WO2009085926A2 (fr) * 2007-12-28 2009-07-09 3M Innovative Properties Company Procédé de fabrication de nanoparticules de zircone
DE102008017216B4 (de) 2008-04-04 2013-08-14 Clariant International Ltd. Kontinuierliches Verfahren zur Herstellung von Fettsäureamiden
DE102008021665A1 (de) * 2008-04-30 2009-11-05 Süd-Chemie AG Verfahren zur Umesterung von Triglyceriden
US8865080B2 (en) * 2008-06-09 2014-10-21 Renewable Energy Group, Inc. Devices, processes and methods for the production of lower alkyl esters
CA2729145A1 (fr) * 2008-06-28 2009-12-30 Edward Bacorn Procedes et systemes de production de combustible en poudre convenant pour la mise a feu dans des exploitations agricoles
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DE102009042522A1 (de) 2009-09-22 2011-04-07 Clariant International Ltd. Kontinuierliches Umesterungsverfahren
EP2457648A1 (fr) * 2010-11-29 2012-05-30 Yellow Diesel B.V. Production d'esters d'alkyl d'acide gras
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US20200291315A1 (en) * 2017-10-16 2020-09-17 Nippon Soda Co., Ltd. Method for manufacturing bio-liquid fuel
CN111097542A (zh) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 一种固体碱及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB634411A (en) * 1946-07-16 1950-03-22 Unilever Ltd Method of treating low-grade fatty stock to form alkyl esters therefrom
US2521742A (en) * 1946-07-16 1950-09-12 Lever Brothers Ltd Method of treating low-grade fatty materials
US5908946A (en) 1996-08-08 1999-06-01 Institut Francais Du Petrole Process for the production of esters from vegetable oils or animal oils alcohols
US20020035282A1 (en) 2000-03-06 2002-03-21 Suppes Galen J. Carbonate catalyzed alcoholysis of triglycerides
EP1298192A1 (fr) * 2001-09-28 2003-04-02 Sumitomo Chemical Company Limited Méthode et appareil pour la production d'esters de corps gras
WO2005021697A1 (fr) * 2003-08-29 2005-03-10 Nippon Shokubai Co., Ltd. Procede de production d'alkyl esters d'acide gras et/ou de glycerine et composition renfermant lesdits esters
JP2006036817A (ja) * 2004-07-22 2006-02-09 Kimura Chem Plants Co Ltd 脂肪酸エステルの製造方法および製造装置
US20060069274A1 (en) * 2004-09-30 2006-03-30 Dias De Moraes E Silva Reynald Continuous production process for ethyl esters (biodiesel)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3837950B2 (ja) 1998-09-09 2006-10-25 住友化学株式会社 脂肪酸エステルの製造方法および脂肪酸エステルを含む燃料
JP4411370B2 (ja) 1998-10-06 2010-02-10 株式会社Ｃｄｍコンサルティング 油脂類から脂肪酸のアルキルエステルを製造する方法
CA2336513C (fr) 2000-02-17 2010-08-24 Tatsuo Tateno Methode de production d'esters d'acide gras et combustibles contenant un ester d'acide gras
JP4752118B2 (ja) * 2000-02-17 2011-08-17 住友化学株式会社 脂肪酸エステルの製造方法および脂肪酸エステルを含む燃料
JP2001271090A (ja) * 2000-03-24 2001-10-02 Sumitomo Chem Co Ltd 脂肪酸エステルの製造方法および脂肪酸エステルを含む燃料
JP3995429B2 (ja) * 2001-03-30 2007-10-24 株式会社レボインターナショナル 低級アルキルエステルの製造方法
JP4936605B2 (ja) * 2001-04-12 2012-05-23 株式会社レボインターナショナル 脂肪酸アルキルエステルの製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB634411A (en) * 1946-07-16 1950-03-22 Unilever Ltd Method of treating low-grade fatty stock to form alkyl esters therefrom
US2521742A (en) * 1946-07-16 1950-09-12 Lever Brothers Ltd Method of treating low-grade fatty materials
US5908946A (en) 1996-08-08 1999-06-01 Institut Francais Du Petrole Process for the production of esters from vegetable oils or animal oils alcohols
US20020035282A1 (en) 2000-03-06 2002-03-21 Suppes Galen J. Carbonate catalyzed alcoholysis of triglycerides
EP1298192A1 (fr) * 2001-09-28 2003-04-02 Sumitomo Chemical Company Limited Méthode et appareil pour la production d'esters de corps gras
WO2005021697A1 (fr) * 2003-08-29 2005-03-10 Nippon Shokubai Co., Ltd. Procede de production d'alkyl esters d'acide gras et/ou de glycerine et composition renfermant lesdits esters
JP2006036817A (ja) * 2004-07-22 2006-02-09 Kimura Chem Plants Co Ltd 脂肪酸エステルの製造方法および製造装置
US20060069274A1 (en) * 2004-09-30 2006-03-30 Dias De Moraes E Silva Reynald Continuous production process for ethyl esters (biodiesel)

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
CORMA, A., IBORRA, S., MIQUEL, S., AND PRIMO, J.: "Catalysts for the productoin of fine chemicals: Production of food emulsifiers, monoglycerides, by glycerolysis of fats with solid base catalysts", JOURNAL OF CATALYSIS., vol. 173, 1998, USACADEMIC PRESS, DULUTH, MN., pages 315 - 321, XP002456064 *
DATABASE WPI Week 200614, Derwent World Patents Index; AN 2006-130822, XP002415936 *
DEMIRBAS A: "Biodiesel fuels from vegetable oils via catalytic and non-catalytic supercritical alcohol transesterifications and other methods: a survey", ENERGY CONVERSION AND MANAGEMENT, ELSEVIER SCIENCE PUBLISHERS, OXFORD, GB, vol. 44, no. 13, August 2003 (2003-08-01), pages 2093 - 2109, XP004414476, ISSN: 0196-8904 *
GRYGLEWICZ, S.: "Rapeseed oil methyl esters preparation using heterogeneous catalysts", BIORESOURCE TECHNOLOGY., vol. 70, 1999, GBELSEVIER., pages 249 - 253, XP002456065 *
LECLERCQ E ET AL: "TRANSESTERIFICATION OF RAPESEED OIL IN THE PRESENCE OF BASIC ZEOLITES AND RELATED SOLID CATALYSTS", JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, AOCS PRESS, CHAMPAIGN, IL, US, vol. 78, no. 11, November 2001 (2001-11-01), pages 1161 - 1165, XP001073024, ISSN: 0003-021X *
PETERSON G R ET AL: "Rapeseed oil transesterification by heterogenous catalysis", JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, AOCS PRESS, CHAMPAIGN, IL, US, vol. 61, no. 10, October 1984 (1984-10-01), pages 1593 - 1597, XP002170978, ISSN: 0003-021X *
SUPPES, G.J., BOCKWINKEL, K., LUCAS, S., BOTTS, J.B., MASON, M.H. AND HEPPERT, J.A.: "Calcium Carbonate Catalyzed Alcoholysis of Fats and OIls", JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY., vol. 78, no. 2, 2001, USAMERICAN OIL CHEMISTS' SOCIETY. CHAMPAIGN., pages 139 - 145, XP002456063 *
WEYTEN, H.; WILLEMS, L.; ADRIANSENS, W.; VAN GINNEKEN, L., PROC. 8TH MEETING "SUPERCRITICAL FLUIDS", BORDEAUX, 14-17 APR. 2002, 14 April 2002 (2002-04-14), pages 139

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US7897798B2 (en) 2006-08-04 2011-03-01 Mcneff Research Consultants, Inc. Methods and apparatus for producing alkyl esters from lipid feed stocks and systems including same
US8445709B2 (en) 2006-08-04 2013-05-21 Mcneff Research Consultants, Inc. Systems and methods for refining alkyl ester compositions
US8017796B2 (en) 2007-02-13 2011-09-13 Mcneff Research Consultants, Inc. Systems for selective removal of contaminants from a composition and methods of regenerating the same
US8585976B2 (en) 2007-02-13 2013-11-19 Mcneff Research Consultants, Inc. Devices for selective removal of contaminants from a composition
US8466305B2 (en) 2007-09-28 2013-06-18 Mcneff Research Consultants, Inc. Methods and compositions for refining lipid feed stocks
US7943791B2 (en) 2007-09-28 2011-05-17 Mcneff Research Consultants, Inc. Methods and compositions for refining lipid feed stocks
US8070836B2 (en) 2007-10-16 2011-12-06 Wayne State University Combined homogeneous and heterogeneous catalytic transesterification process for biodiesel production
US8975426B2 (en) 2008-05-19 2015-03-10 Wayne State University ZnO nanoparticle catalysts for use in transesterification and esterification reactions and method of making
US8163946B2 (en) 2008-05-19 2012-04-24 Wayne State University Methods and catalysts for making biodiesel from the transesterification and esterification of unrefined oils
US8895764B2 (en) 2008-05-19 2014-11-25 Wayne State University ZnO nanoparticle catalysts for use in biodiesel production and method of making
CN101624533A (zh) * 2008-07-12 2010-01-13 程文波 一种生物柴油生产中酯交换反应方法及其装置
US8361174B2 (en) 2008-10-07 2013-01-29 Sartec Corporation Catalysts, systems, and methods for producing fuels and fuel additives from polyols
US9102877B2 (en) 2008-11-12 2015-08-11 Sartec Corporation Systems and methods for producing fuels from biomass
DE102009006777A1 (de) 2009-01-30 2010-08-05 Wolfgang F. Prof. Dr. Hölderich Verfahren zur Herstellung von Fettsäureestern und Glycerin durch Umesterung von pflanzlichen und tierischen Fetten und Ölen
WO2010085947A1 (fr) 2009-01-30 2010-08-05 Hoelderich Wolfgang Friedrich Procédé de production d'esters d'acides gras et de glycérol par transestérification de graisses et d'huiles végétales et animales
AT513799A1 (de) * 2012-12-18 2014-07-15 Klaus Mag Schell Verfahren zur Herstellung eines Bio-Diesel-Kraftstoffes mit einem speziell ausgelegtem Reaktor und quasi autokatalytisch wirksamer nanoskalig strukturierter Materialoberfläche des Reaktors
WO2014094007A2 (fr) 2012-12-18 2014-06-26 Gerhard Nauer Procédé de production d'un carburant biodiesel à l'aide d'un réacteur de conception spéciale, dont le matériau présente une surface à structuration nanométrique ayant un effet „(auto)catalytique"
AT513799B1 (de) * 2012-12-18 2020-02-15 Mag Schell Klaus Verfahren zur Herstellung eines Bio-Diesel-Kraftstoffes mit einem speziell ausgelegten Reaktor und quasi katalytisch wirksamer nanoskalig strukturierter Materialoberfläche des Reaktors
US10239812B2 (en) 2017-04-27 2019-03-26 Sartec Corporation Systems and methods for synthesis of phenolics and ketones
US10544381B2 (en) 2018-02-07 2020-01-28 Sartec Corporation Methods and apparatus for producing alkyl esters from a reaction mixture containing acidified soap stock, alcohol feedstock, and acid
US10696923B2 (en) 2018-02-07 2020-06-30 Sartec Corporation Methods and apparatus for producing alkyl esters from lipid feed stocks, alcohol feedstocks, and acids

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PL2044183T3 (pl) 2014-05-30
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